Metal-containing dyestuffs



United States Patent ()fi ice 3,375,240 Patented Mar. 26, 196 8 METAL-CONTAINING DYESTUFFS Fabio Belfa, Basel, Paul Lienhard, Riehen, and Eginhard Steiner, Basel, Switzerland, assignors to J. R. Geigy A.G., Basel, Switzerland No Drawing. Filed Oct. 5, 1964, Ser. No. 401,664 Claims priority, application Switzerland, Oct. 11, 1963,

12,538/ 63 9 Claims. (Cl. 260-145) ABSTRACT OF THE DISCLOSURE Metal complex dyestulis of good dyeing properties consisting essentially of a mixture of (a) a bicyclically metallized dyestutf moiety and (b) a bicyclically metallized formazane moiety, the mixture being complexed with Co or Cr as the metal, and molar ratio of (a) to (b) ranging from 2:1 to 1:2. Moiety (a) is the residue of a monoazo dye, of a disazo dye or of an azomethine dye.

The present invention concerns new metal-containing dyestuffs, processes for the production thereof, their use for the coloring, and especially the dyeing-of polyarnidetype fibers as well as, as industrial products, the materials dyed with the aid of these dyestuffs.

It is known that valuable chromiumand cobalt-containing dyestufis are obtained if an agent giving o'lfchror'nium or cobalt is reacted with an azo, az'omethine or formazane dyestufi capable of forming bicyclic metal complexes, whereby chromiumor cobalt-complex compounds which contain two molecules of azo,-azomethine-or'formazane dyestuff bound bicyclically to one chromium or cobalt atom are obtained.

It has now been found that new chromiumor cobaltcontaining dyestuffs having very good dyeing properties, in particular very good color yield, great fastness to light and unexpectedly high water solubility, are obtained by reacting at least one azo or azomethine compound capable of forming bicyclic heavy metal complexes, preferably an azo compound and at least one fo'rmazane compound forming bicyclic heavy metal complexes, with an agent giving 01f chromium or cobalt to form a complex compound which contains one molecule of bicyclically bound azo or azomethine compound andone molecule of bicyclically bound formazane compound bound to one atom of chromium or cobalt.

Because of the greatly dilfering constitutions of azo and azomethine dyestuffs on the one hand and of formazane dyestutfs on the other, it'would have been expected that only symmetrical azo or azomethjne' andsymmetrical formazane complex dyestulfs would be formed-;therefore the formation of unsymmetrical complex dyestuffs of the type defined is very surprising.

Azo compounds forming bicyclic'metal complexes ar'e" chiefly those which correspond to the formula series containing the s'ubstituent HX in a position adjacent to the azo bond,

E represents the radical'of a coupling component coupled in a position adjacent to \HX',

XH represents the hydroxyl of carboxyl group or a substituent which can be converted into such a group, and

XH rep-resents the hydroxyl group or the primary or a secondary amino group.

Preferably, D is a radical of the benzene series; B" is for example the radical of a benzene, naphthalene" or 1'-arylpyrazole compound. 7

D and E can contain the substituents usual in dyestuffs, for example, nucleophilic substituents such as hydrocarbon, particularly lower alkyl groups, ether groups, preferably lower alkoxy groups, acylamino, especially alkanoylamino groups, or electrophilic substituents such as halogens, e.g. fluorine, chlorine or bromine, carboxyl and sulfonic acid groups, as well as functional derivatives thereof, e.g. carboxylic acid and sulfonic acid amide groups optionally substituted at the nitrogen atom, carboxylic acid and sulfonic acid ester groups, the nitro, cyano'or trifluoromethyl group, arylaz'o groups or acyl groups such as lower alkanoyl, aroyl, especially benzoyl, lower alkylsulfonyl or arylsulfonyl, especially phenylsulfon'yl groups.

The" aromatic rings" which may occur in these substitu ents can also be correspondingly substituted.

Lower alkoxy groups or acyloxy, especially phenyl sulfonylox'y groups such as the p-methylphenylsulfonyloxygroup, are examples of the case when X-H in Formula I is a substituent which can be converted into a hydroxyl group. If X aH is a substituent which can be converted into a carboxylgroup, then it is, for e x'ample,a carboxylic acid ester group, particularly a lower alkoxy carbonyl group.- 7 I Preferably X--H is the hydroxyl group-and HX is the hydroxyl, the primary amino or a lower alkylamind group the alkyl radical of which can be substituted, for instance, by hydrox'yl or lower alkox'y'. I

Preferred azomethine compounds forming bicyclic metal complexes are those of the forrruila.

wherein D" and E each represent" a r'e'rdical of the benzene or naphthalene serie's containing HX" or the hydroxyl group in a position adjacent to the azomethine' bond,

H'"X- represents" the carboxyl group or, preferably, the

hydroxyl group.

D and E are preferably radicals of the benzene series.

The azomethine dyestuffs of Formula H can contain the substituents usual in dyestuffs, in particular those mentioned in the description of" azo dyestulfs of Formula I.

D represents a radical of the benzene or naphthalene Such azomethi'ne compounds are obtained by the usual methods by condensing an o-aminopheiiol or o-aminonaphthol with an o-hydroxyaldehyde of the benzene or naphthalene series.

As formazane compounds usable according to the invention, fundamentally all form'azan'es forming" co-ordinative trivalent metal complexes are used. Formazane compounds which are particularly favorable are those of the formula wherein If R is an unsubstituted alkyl radical, then this advantageously has 1 to 7 carbon atoms As defined, this radical can contain inert substituents, e.g. halogen, such as fluorine or chlorine, the hydroxyl, cyano or a low alkoxy group. When R is an alkenyl radical it chiefly contains 2 to 4 carbon atoms; if R is a carbocyclic aromatic radical then it is chiefly a radical of the benzene or naphthalene series. If R is a heterocyclic aromatic radical this has, in particular, 5- or 6- ring members and as hetero atoms it preferably contains nitrogen, oxygen and/ or sulphur. These heterocycles can form condensed rings either among themselves or with carbocycles. If R is an acyl radical then it is particularly an aliphatic carboxylic acid radical such as acetyl, propionyl or a butyryl, the radical of a homocyclic aromatic carboxylic acid such as benzoic acid, or of an organic sulfonic acid such as methane sulfonic acid or benzene sulfonic acid, or of a carbamic acid containing an N-carbocyclic aromatic substituent.

Preferably A and B are each a radical of the benzene series and R is a radical of the benzene or naphthalene series.

. The formazane dyestulfs of Formula III can contain the ring substituents usual in dyestuffs, for example the substituents mentioned more in detail hereinafter. It is particularly advantageous if these forrnazanes contain water solubilizing groups, in particular one or more sulfonic acid, sulfonic acid amide and/or low alkylsulfonyl groups, preferably methylsulfonyl or ethylsulfonyl groups.

-The formazanes of Formula III are obtained by methods known per se. For example, an aldehyde is condensed with the hydrazine from one of the two amines HX'ANH or B-NH (preferably with the hydrazine obtained from the amine BNH to form the hydrazone and this is coupled with a diazonium compound from the other amine. Or, for example, an equivalent of' a diazonium compound from one of the amines given above is coupled with one equivalent of a methylene or methine compound which can be coupled twice while splitting off 2 groups or 1 group which can easily be splitofi or groups which can be converted into such groups, such as the formyl, acetyl, carboxylic acid group or a carboxylic acid ester, amide or nitrile group.

A preferred group of cobalt metal-complex dyestufis according to the invention are those in which a dyestuif of Formula I or II is complexed with cobalt and with one of the following forrnazane dyestuffs falling under Formula-III:

(a) Formazanes of the formula wherein each of R and R represents, independently of (IIIA) 4 the other R, hydrogen, lower alkyl, cyano-lower alkyl, hydroxy-lower alkyl or lower alkoxy-lower alkyl;

Q represents a bridge member which is phenylenesulfonyl, N-phenylene-aminosulfonyl, or N-lower alkyl- N-phenylene-aminosulfonyl, said bridge member being linked via its sulfonyl moiety to the ring B A represents one of the radicals of the formulas O H lower alkoxy-(F O I I S O 2- (lower alkyl) X being nitrol, chloro, bromo, alkyl of from 1 to 5 carbon atoms, lower alkyl-sulfonyl, lower alkanoylamino, N-lower alkyl-N-lower alkanoylamino, lower alkylsulfonylamino or N-lower alkyl-N-lower alkylsulfonylamino;

X being chlorine, bromine or lower alkylsulfonyl,

X being chlorine, bromine, nitro or lower alkylsulfonyl,

' X being nitro or lower alkylsulfonyl,

X being chlorine, or nitro,

Y'represents hydrogen, chlorine, bromine, lower alkyl, lower alkoxy or nitro,

D represents CO or SO and p is an integer ranging from 1 to 2.

' Y (b) Formazanes of the formula R: (IIIB) wherein each of R and R represents, independently of the other R, hydrogen, lower alkyl, cyano-lower alkyl, hydroxy-lower alkyl or lower alkoxy-lower alkyl;

Q represents a bridge member which is phenylenesulfonyl, N-phenylene-aminosulfonyl, or N-lower alkyl- N-phenylene-aminosulfonyl, said bridge member being linked via its sulfonyl moiety to the ring A;

p is an integer ranging from 1 to 2,

X is hydrogen or nitro;

X is hydrogen, nitro, chlorine, bromine, lower alkoxy or lower alkyl; and

Y is hydrogen, chlorine, bromine, lower alkyl, lower alkoxy or nitro;

rIro wherein each of R R R and R represents, independently of the other Rs, hydrogen, lower allryl, cyanolower alkyl, hydroXy-lower alkyl or lower alkoXy-l'ower alkyl,

Each of Q and Q represents a bridging member which is phenylenesulfonyl, N-phenylene-aminosulfonyl, or N- lower alkyl-N-phenylene-aminosulfonyl, said bridging member being linked via itssulfonyl moiety to the rings Aand B, respectively,

Of pand p one is l and the other is an integer'ran'ging from 1' to 2,

Y represents hydrogen, chlorine, bromine, lower alkyl, lower alkoxy or nitro, I

And X represents hydrogen or'nitro.

(d) Formazanes of the formula SO2N\ R, (IIID) wherein each of R and R represents, independently of the other, hydrogen, lower alkyl, cyano-Iower alkyl, hydroxy-lower alkyl or loweralkoxy-lower alkyL- And wherein A and X5, have the meanings given hereinbefore; or

(e) Formazanes of the formula X3! rIIE wherein A is one of the radicals alkyl sullonyl OH X represents hydrogen, lower alkanoylamino, lower alkoxy-carbonylamino, lower alkylsulfonylamino, lower alkylsulfonyl or nitro.

X represents hydrogen, chlorine, bromine, lower a1- kyl, .low'era'lkoxy or nitro, I v

X represents hydrogen, lower alkoxy, lower alkyl, chlorine'or bromine,

R represents hydrogen, or lower alkyl,

Z represents alkyl, mono-chloro-methyl or trifiuoromethyl, 7 g g and each of m and n is an integer ranging from 1 to 2. Lower used in this specification and the appended claims in connection with an aliphatic radical means that this radical has at least one and not more than 4 carbon atoms.

According to a first, preferred aspect of the invention a cobalt metal complex dyestufl which is pr'eferably'capable of dyeing p'olyamide-type fibers from a neutral to weakly acid bath is obtained by reacting (a) an agent giving off cobalt simultaneously with (b) at least one azo dyesturf or azomethine dyestuff c'ompound which forms bicyclic metal complexes and (c) at least one formazane compound which forms bicyclic metal complexes,

lie

in the case of the reactant (Ii) being an azo dyestufl? com- X- o A 0 1k (IV) pound; or of the formula DN=CHE' (v) in the case of reactant (b) being an azomethine dyestufi? compound.

Thereaction is preferably'performed in the presence of an acid binding agent such as sodium or potassium acetate or carbonate. Suitable reaction media are e.g. amides of lower 'fatty acids such as formamide or dimethyl formamide, or higher boiling alcohols such as alkanols of from 3 to 7 carbon atoms or alkylene glycols or their lower mo'noalkyl ethers such as Cellosolve. If necessary, the reaction can also be performed in the presence of compounds which form soluble complex compounds with the chromium or cobalt salts in an alkaline medium, for example in the presence of tartaric acid, citric acid, lactic acid or salicylic acid.

The above-defined content of mixed complex compounds of Formulas 1V or V, respectively, is attained by using the reactants (b) and (c) in a suitable molar ratio which is in the range between the ratios 4:1 and 1:4, and preferably at approximately 1:1.

According to another aspect of the invention, a chromium metal complex dyestutf the formula of which is equal to Formulas IV or V, except that the central cobalt atom is replaced by a chromium atom, is obtained in a similar manner, but using as reactant (a) an agent giving off chromium. Preferably, however, the production of a chromium metal mixed complex dyestufi which is preferably capable of dyeing polyamide-type fibers from a neutral to weakly acid bath, is carried out according to a third aspect of the invention, which comprises (a) First reacting (i) An agent giving off chromium with (ii) At least one azo or azomethine dyestulf as defined to form a chromium complex compound which contains one molecule of the dyestuff mentioned to one chromium atom, this reaction step being preferably performed at temperatures of l-140 C., in an open vessel or under excess pressure above ambient pressure, in particular in water or in an organic solvent such as an alcohol, and in an acid medium; and then i (b) Reacting the resulting 1:1 chromium complex compound with (iii) At least one formazane dyestuff as defined in Formula III to form a chromium complex compound containing one molecule of bicyclically bound azo or azomethine compound and one molecule of bicyclically bound formazane compound to one chromium atom, this second step being also advantageously performed in aqueous or organic reaction medium, but in a neutral or, often more advantageously, in an alkaline pH range in the presence of acidbinding agents such as potassium or sodium acetate, carbonate or dilute sodium or potassium hydroxide solution.

In this case, the content of mixed chromium complex dyestuif compound of the formula XIII I.

t r i N (v1) or of the formula cobalt with the azo, azomethine and formazane compounds as defined is performed depending on the mode of operation chosen, e.g. in aqueous slurry, solution or in the melt, e.g. in the melt of the alkali metal salt of a low fatty acid, advantageously however, in an organic solvent.

Mixtures of such metal-containing mixed complex compounds according to the invention can be produced by the process according to the invention by treating two or more of the mixtures of dyestuff reactants of Formulas I, II and III defined above with suitable proportions of agents giving off chromium or cobalt of the type defined.

Polyamide-type fiber materials dyed with the cobalt and chromium mixed complex dyestuffs according to the invention are distinguished in particular by their fastness to light, wet fastness including fastness to washing, milling, alkali and sea water, and fastness to rubbing and decatizing, as well as by the level aspect due to uniformity of the dyeings.

The new metal-containing dyestuffs which contain no water solubilizing groups can be'us'ed for the dyeing of plastics, lacquers, varnishes or spinning masses obtained from acetyl cellulose or polyamides.

Those dyestulfs according to the invention which contain water-solubilizing groups such as carboxylic acid or phosphonic acid and, mainly, sulfonic acid groups, are suitable for the dyeing and printing of organic fibers, particularly those containing polyamide, e.g. natural polypeptide material such as leather, wool or silk, or synthetic polyamide fibers such as nylon or polyurethane fibers. For the dyeing of this type of material, those chromiumor cobalt-containing dyestuffs according to the invention are particularly suitable which contain at most one sulfonic acid group; they are distinguished by an unexpectedly high water-solubility; in many cases they draw onto this material even from a neutral to weakly acid bath. Another valuable group is formed by those dyestuffs according to the invention which contain no groups which dissociate acid, in particular no carboxylic acid or sulfonic acid groups apart from those taking part in the complex formation, but owe their water solubility to low alkylsulfonyl groups, the sulfonic acid amide group, and to the sulfonic acid amide groups substituted by low aliphatic radicals. These dyestufls have very good aflinity to wool and polyamide material having dyeing properties similar thereto and they draw completely onto such material from even a neutral to weakly acid bath.

In many cases the water solubility of such dyestuffs containing no sulfonic acid groups can be favorably aifected by admixture with anion-active or non-ionogenic wetting or dispersing agents.

The invention is further illustrated by the following non-limitative examples. Where not otherwise expressly stated, parts and percentages are given therein by weight. The temperatures are in degrees Centigrade. The relationship of parts by weight to parts by volume is as that of grams (g.) to milliliters (ml.).

Example 1 Cobalt Complex OH OH 1 Ho-o-ol-jt N=NC=NNH SOENH: N=Ni 1 r I NH NO: S 2 2 s 15 parts of cobalt acetate (corresponding to 3.54 parts of cobalt) are added at 85 .to 22 parts of the formazane dyestulf obtained by coupling an equimolecular amount of 4-nitro-2-diazo 1 hydroxybenzene with the benzaldehyde phenyl hydrazone-3-sulfon-ic acid amide and 21.2 parts of the monoazo dyestutf obtained from Z-diazochloranilide, to 'which dyestuff mixture 300 parts of formamide have been added. The whole is kept at 80- 85 until metal complex formation is complete. The cobalt-containing dyestuif is precipitated by the addition of sodium chloride solution, filtered oil and dried.

It is a dark powder which dyes wool from a neutral to weakly acid bath in yellowish olive green shades. The dyeings are of great depth of shade, and have good wet fastness properties and very good fastness to light.

By using in the above example, the formazane dyestutf and azo dyestufi in amounts of 13.2 and 29.7 parts, respectively, instead of 22 and 21.2 parts, with otherwise the same procedure, a more yellowish dyestuff is obtained. A more greyish dyestuff also having good properties is obtained by using in this example the formazane dyestuff and the azo dyestuif in amounts of 30.8 parts and 12.7 parts, respectively, and otherwise following the same procedure.

Dyestuffs having similar properties are obtained if in the above example, the dyestuif from Z-diazo-l-hydroxybenzene-4-ethyl sulfone and acetoacetic acid-o-chloranilide is replaced by 21.2 parts of monoazo dyestufi from 2-diazo- 1-hydroxybenzene-4-ethyl sulfone and acetoacetic acid-mchloranilide or by 19.5 parts of monoazo dyestuff from 2- diazo-1-hydr0xybenzene-4-ethyl sulfone and acetoacetic acid anilide or by 18.8 parts of monoazo dyestuif from 4- nitro-2-diazo-l-hydroxybenzene and acetoacetic acid-ochloranilide.

15 parts of cobalt acetate (corresponding to 3.54 parts of cobalt) are added at 80-85 to 24.2 parts of formazane dyestuff and 15.5 parts of monoazo dyestuif in 300 parts of dimethyl formamlide. The formazane dyestuff obtained by coupling 4-nitro-2-diazo-1-hydroxybenzene with benzaldehyde phenylhydrazone-3 sulfonic acid-N- -(/8-hydroxyethyl)-amide, and the monoazo dyestufi is formed from S-nltro-Z-diazo-l-hydroxybenzene and 2-hy- 'd roxynaphthalene. The mixture is kept at 80-85 until no more starting dyestuifs can be detected. The cobaltcOn-tain-ing dyestufi is then precipitated by the addition of sodium chloride solution, filtered 01f, washed with dilute sodium chloride solution and dried. It is a dark powder which dyes wool from a neutral bath in navy blue shades. The dyeings'have very good light and wet fastness properties, great depth of shade and good fast- "ness to rubbing.

Similar dyestutfs .are obtained if in this example the formazane dyestuIT from 4-nitro-2-diazo-Lhydroxy-ben- .zene and benzaldehyde phenylhydrazone-B-sulfonic acid- N-(B-hydroxyethyD-amide is replaced by 22 parts of formazane dyestuif from 4- itro 2-diaz orl-hydroxybenzene and benzaldehyde phenylhydrazone-3- or -4-sulfonic acid amide.

10 Exampl 3 Chromium Complex N=NC=NNH 22.2 parts of the complex chromium compound of the type containing 1 chromium atom to l dyestuff molecule, which compound consists of 2.6 parts of chromium and 19.7 .parts of the monoazo dyestuff obtained from diazotized 1-amino-Z-hydroxynaphthalene-4-sul-fonic acid and Z-hydroxynaphthalene, are added to 333 parts by volume of forma-m ide. 17.2 parts of formazane dyes-tuflf from diazotized Z-aminobenzene-1-carboxylic acid and benzaldehyde phenyl hydrazone are added to this solution. 15 parts of calcined sodium carbonate are added to the mixture which is then heated at 100105 until the starting dyestuffs have disappeared. The chromium-containing dyestufi is precipitate-d by the addition of saturated sodium chloride solution, filtered ofi, washed with dilute sodium chloride solution and dried.

It is a dark powder which dyes Wool and silk from a neutral to weakly acid bath in grey shades which have imil g d fastness p p r ies as he dyeiugs ob ained in the preceding examples. Y J

Similar dyestuffs are obtained if, in this example, the fiormazane dyestuif from diazotized Z-aminobenzene-L ca-rboxyliic acid and benzaldehyde .phenyl hydrazflne is replaced by 25 parts of formazane, dye-stuff from diazotized Z-aminobenzene-l-carboxylic =acid-5-sultonic acid anilide and benzaldehyde phenyl hydnazone, 25.7 parts of formazane dyestuff from (llaZjQtlZCd Zamino benZenee l-carboxylic aeid-S-sulfonic acid-N-methyl anilide and benzaldehyde phenyl hydrazone or 22.8 parts of formazane dyestufl from diazotized 4-hyd-roxy-3aminodiphenyl sulfone and benzaldehyde phenyl hydrazpne.

Example 4 17.7 parts of azomethine dyestuff (obtained by condensation of 4-hydroxy-3-aminodiphenyl sulfone and salicylaldehyde) in 300 parts of formamide are added to 22 parts of formazane dyestuif. obtained by coupling equimolecula-r amounts of 4-n itro-2 diazo-l-hydroxybenzene with benzaldehyde phenyl hydrazone-4-sulfonic acid amide and, at -85 15 parts of cobalt acetate, corresponding to 3.54 parts of cobalt, are added. The whole is stirred at this temperature until metal complex formation is complete. The metal-containing dyestutf is precipitated by dilution with concentrated sodium chloride solution, then filtered off, washed with dilute sodium chloride solution and dried. It is ada-rk powder which dyes wool firom a neutral to Weakly acid bath in beautiful olive green shades which hav imilar go d .fa tn s pr p rties a the dyeings obtained in the preceding examples,

Similar dy s uif are o t i ed if, in this example, the azomethine dyestutt from 4-hydroxy-3-aminodiphenyl sul- Example Cobalt complex iizHs 23.7 parts of formazane dyestulf obtained by coupling equimolar amounts of 4-nitro-6-chloro-2-diazo l hydroxybenzene with benzaldehyde phenyl hydrazone-3-sulfonic acid amide and 19.3 parts of monoazo dyestuff from 2-diazo 1-hydr0xybenzene-4-ethyl sulfone and l-phenyl- 3-methyl-5-pyrazolone in 300 parts of formamide are heated at 8085 with parts of cobalt acetate, corresponding to 3.54 parts of cobalt, until metal complex formation is complete.

The cobalt-containing dyestuflf is then precipitated by the addition of concentrated sodium chloride solution, filtered off, washed with dilute sodium chloride solution and dried. After drying, it is a dark powder which dyes wool from a neutral to weakly acid bath in brown-olive shades. The dyeings are level, of good depth and have high grade wet fastness and very good light fastness properties.

Similar dyestuffs having the same high grade fastness properties are obtained if, in this example, the monoazo dyestuif from 2-diazo-1-hydroxybenzene-4-ethyl sulfone and l-phenyl-3-methyl-5 pyrazolone is replaced by parts of the monoazo dyestuff from 2-diazo-1-hydroxybenzene-4-n-propyl sulfone and 1-phenyl-3-methyl-5-pyrazolone, by 18.6 parts of the monoazo dyestuff from Z-diaZo-l-hydroxybenzene-4-sulfonic acid amide and 1- phenyl-3-methyl-5-pyrazolone, by 17 parts of the monoazo dyestulf from 4-nitro-2-diazo-l-hydroxybenzene and 1-phenyl-3-methyl-5-pyrazolone or by 16.4 parts of the monoazo dyestufi from 4-chloro-2-diazo-l-hydroxybenzene and 1-phenyl-3-methyl-5-pyrazolone.

Example 6 Cobalt complex 15 parts of cobalt acetate (corresponding to 3.54 parts of cobalt) are added at 8085 to 21.5 parts of formazane dyestulf, obtained by coupling equimolecular amounts of 4-chlor0-2 diazo l hydroxybenzene and benzaldehyde phenyl hydrazone-3 -sulfonic acid amide, and to 15.4 parts of monoazo dyestutf obtained by coupling 4-nitro- 2-diazo-1 -hydroxybenzene and 2 aminonaphthalene, which dyestuif mixture is in 300 parts by volume of 12 formamide. The whole is kept at this temperature until no more starting dyestulfs can be traced.

The cobalt-containing dyestuff is precipitated from the reaction mixture by diluting it with concentrated sodium chloride solution. It is then filtered olf, washed with dilute sodium chloride solution and then dried.

After drying it is a dark powder which dyes wool from a neutral to weakly acid bath in olive grey shades of similar good fastness properties as the dyeings obtained in the preceding examples.

It in the above example, the monoazo dyestufi from '4-nitro-2-diazo-l-hydroxybenzene and 2 aminonaphthalene is replaced by 16.8 parts of monoazo dyestufi from 4-nitro-2-diazo-1-hydroxybenzene and 2-ethylaminonaphthalene or by 17.6 parts of the monoazo dyestuif from 4-nitro-2diazo-l hydroxybenzene and 2-(fl hydroxyethyl)-aminonaphthalene or by 19.2 parts of the monoazo dyestuff from 4-nitro-2-diazo-1-hydroxybenzene and 2-phenylaminonaphthalene, then dyestufis having similar properties are obtained.

Example 7 .Cobalt complex 27.3 parts of formazane dyestutf obtained by coupling equimolecular amounts of 5-nitro-2-diazol-hydroxybenzene-4-ethyl sulfone with benzaldehyde phenyl hydrazone-4-sulfonic acid-N-methylamide and 19.1 parts of disazo dyestutf obtained from 3-hydroxy-6-methyl-4-diazobenzene and Z-hydroxynaphthalene, are heated at in the presence of 300 parts by volume of dimethyl formamide, with 16 parts of cobalt acetate, corresponding to 3.54 parts of cobalt, until no more starting dyestuifs can be detected.

The cobalt-containing dyestutf is precipitated by diluting the reaction mixture with concentrated sodium chloride solution, and is then filtered oil and dried.

After drying, it is a dark powder which dyes wool from a weakly acid or neutral bath in level olive-blue shades which have similar good fastness proper-ties as the dyeings obtained in the preceding examples.

The corresponding chromium complex which is produced in the same manner as in the preceding example, but using an equivalent amount of chromium acetate in lieu of cobalt acetate, an equimolar amount of formamide in in lieu of dimethyl formamide, and a temperature of -105 in lieu of 80-85 C., dyes wool under similar dyeing conditions olive-grey shades of similar good fastness properties.

' Example 8 2 parts of the dyestufi according to Example 2 are dissolved in 4000 parts of water and, at 40-50, 100 parts of previously wetted wool are introduced into the dyebath. The bath is brought to the boil within half an hour, kept at the boil for 45 minutes and then the wool is rinsed with cold water and dried.

. The navy blue dyeing obtained has very good wet and light fastness properties.

If the formazane dyestuffs given in column 11 of the 13 following Table I are reacted with the azo or azomethine compound given in column III and with a soluble salt of the metals given in column IV by the methods de- 14 scribed in the previous examples 1 to 7, then similarly valuable dyestuffs are obtained, the metal complexes of which produce on wool the shades given in column V.

TABLE I I II II No. Formazane compound irom- Azo or azomethine compound from 9 4-nitro-2-diazo-l-hydroxybenzene benzaldehyde 4-m'tro-2-diazo-1-hydroxybenzene 2-aninonaphphenyl hydrazone-Zi-sulphonic acid amide. thalene. 10 do 4-nitro-2-diazo-1-hydroxybenzene 2-(B-hydroxy ethyD-aminonaphthalene. 11 do 4-nitro-2-diazo-1-hydroxybenzene-d-phenyl-3- methyl-5-pyrazolone. 12 do 4-nitro-2-diazo-l-hydroxybenzene l-phenyl-3- I methyl-5-pyrazolone-(3'-sulphonic acid amide). 13 ..do 4-11itr0-2-diazo-l-hydroxybenzene acetoacetic acid anilide. 14 ..do 4-nitro-2-diazo-1-hydroxybenzene 2-hydroxynaphthalene. 15 .d0 4-nitro-2-diazo-l-hydroxybenzene 1-phenyl-3- methy1-5-pyrazolone-3-sulphonic acid. 16 ..do 4-nitro-2-diuzo-l-hydroxybenzene-el-(3'-nitr0- phenyl)-3-methyl-5-pyrazolone. 17 d0 4,6-dinitro-2-dlazo-l-hydroxyhenzene 2-hydroxynaphthalene. 18 .d0 2-diaz0-1-hydroxybenzene-4-ethylsulphonewlphenyl-3-methy1-5pyrazclone. 19 do 2rdiazo-l-hydroxybenzene-4-ethylsulphone 1- (3-chlorophenyl)-3-methyl;5-pyrazolone. 20 ..d0 2-diaz0-l-hydroxybenzene-4ethylsulphonel- (4-methoxyphenyl)-3-methyl-5-pyrazolone. 21 ..do 2-diazo-1-hydroxybenzene-4-ethylsulphone-v2- hydroxynaphthalene. 22 ..do 4-chloro-2-diazo-l-hydroxybenzene-d-phenyl-Zimethyl-S-pyrazolone. 23 ..d0 4,6-dim'tro-2-diazo-1-hydroxybenzeneeLphenyI-d methyl-fi-pyrazolone. 24 ..do z-diazo-l-hydroxyhenzene-l-methylsulphone-1- (4-methylphenyl)-3-methyl-5-pyrazolone. 25 ..d0 4-phenylsu1phonyl-2-diazo-l-hydroxybenzene-3- sulphonic acid amide- 2-hydroxynaphthalene- 6-sulphonic acid amide. 2-diazo-l-hydroxybenzeneA-sulphonic acid- 2- hydroxynaphthalene. fi-nitro-l-diazo-Z-hydroxynaphthalene-4-sulphonic acid 2-hydroxynaphthalene. 4-pheny1azo-2-amino-1-hydroxybenzene+5-nitro Z-hydroxybenzaldehyde. 2-diazo-1-hydroxybenzene-4-sulphonic acid (2- carboxyphenyl)-amide- 2-hydroxynaphthalene.

4-nitro-2-diazo-1-hydroxybenzene+4-chloro-2- 5-nitro-2-diazo 1-hydroxybenzene- 2-hydroxydiazo-1-hydroxybenzenebenzaldehyde phenyl naphthalene. hydrazone-i-sulphonic acid amide. 31 do 5-nitro4-chloro-2-diazod-hydroxybenzene 2- hydroxynaphthalene. 32 do 5nitro2-diazo-l-hydroxybenzene+5-nitro-4- chloro-Z-diazo-1-hydroxyhenzene- 2-hydroxynaphthalene. 33 2-diazobenzene carboxylic acidbenzaldehyde- 1 diazo-2-hydroxynaphthalene-4-sulphonic acid 2,5-dichlorophenyl hydrazone. 2-hydroxynaphthalene. 34 2-diazobenzene carboxylic acid 2,6-dichlorobenzdo aldehyde-2,5-dichloropheny1 hydrazone. 35 2-diazohenzene carboxylic acid benzaldehyde-3- 4-m'tro-2-diazo-l-hydroxybenzene- 1-acetylamino-7- ghlgro-fi-(4'-chloro-2-sulpho)-phenoxyphenyl hydroxynaphthalene.

y razone. 36.... 2-diazobenzene carboxylic acid-5-sulphonie acid 2-diazo-l-hydroxybenzene-4-methylsulphone- 1- amidebenzaldehyde phenyl hydrazone. carbomethoxyamino-7-hydroxynaphthalene. 37... 4-nitro-2diazo-l-hydroxybenzenebenzaldehyde 2diazo-l-hydroxybenzene-4-ethylsulphonefilphenyl hydrazone--sulphonic acid amide. phenyl-3-methyl-5-pyrazolone. 38 do 2-diazo-1-hydroxybenzene-4-ethylsulphone 2- hydroxynaphthalene. 39 do u... 2-diazo-l-hydroxybenzene-4-ethylsulphoneacetoacetic acid-o-chloranilide. 40 do 4-nitro-2-diazo-1-hydr0xybenzene-rl-phenyl-(imethyl-5-pyrazolone. 41 ..d0 2-diazo-l-hydroxybenzene-4-ethylsulphone-dphcnyl-3-methylpyrazolone+acetoacetic acid-ochloranilide. 42 N-di-(methylsulphonyl)-amino-2-diazohenzene 5-nitro-2-diazo-l-hydroxybenzene 2-hydroxynaphbenzaldehyde phenyl hydrazone-3-sulphonic acid thalene. amide (saponified). -43 4-nitro-2-diazo-l-hydroxybenzene benzaldehyde y .-..do

phenyl hydrazonei-sulphom'c acid-N,N- bis-(B- hydroxyethyl)-amide. 44 6-acetylamino-2-diazo-l-hydroxybenzeneA-methyl- .-...do

suiphone-benzaldehyde phenyl hydrazone-Iisulphonic acid amide. 45 .do 4-m'tro-2-amin0-1-hydroxybenzene-i-Z-hydmxy-lnaphthaldehyde,

46 5-nitro-2-diazo-l-hydroxybenzene4-ethyl sulphon'e '2-diazo-1-hydroxybenzcne-4-ethyl sulphone 1- iuriurolphenyl hydrazone-B-sulphonic acid amide. phenyl-B-methyl-fi-pyrazolone. 47 do 2-diazo-l-hydroxybenzene-4-ethylsulphonel-(3- chlorophenyl)-3-methyl-5-pyrazolone. 48 4-chloro-2-diazo-l-hydroxybenzeneficyclohexyl- ....do

aldeiyde phenyl hydrazone-3-sulphonic acid am1 e. 49 do 2-diazo-l-hydroxybenzene-4-ethyl sulphone 1- phenyl-3-methyl-5-pyrazolone. 50.... 2-diazo-i-hydroxybenzene-4-phenglsulphone-3- -do sulphonic acid amidebutyral ehydephenyl hydrazone-S-sulphonic acid amide. 1 a 51 2-diazo-l-hydroxybenzeneA-phenylsulphone-Ii- -do sulphonic acid amidecrotonaldehyde phenyl hydrazoneQ-sulphonic acid amide.

IV v Metal Shade of metal complex on W001 Co Olive-grey.

O0 Do.

00 Khaki.

C0 Do,

0 Yellovvish olive green. 00....-. Violet brown.

.- Khaki.

Black.

Olive khaki.

Raisin.

Olive brown. I

O0 Brown.

' Co Olive brown.

Co Brown-violet.

Cr Violet-grey. Gr Grey-black.

Co Khaki.

Co Raisin.

(30..-... Navy blue.

Cr Grey.

Cr Olive grey.

Cr D0.

Cr Do.

00 Olive-brown.

C0 Raisin.

Co Olive green.

00 Yellowish olive green.

00 Olive green.

Co Navy blue.

Co Do.

Co Do.

00--.... Kkaki.

00......01ive.

Co Do.

Co Do.

22 parts of formazane dyestutf, obtained by coupling diazotized 4-nitro-2-amino-l-hydroxybenzene with benzaldehyde phenyl hydrazone-3-sulfonic acid amide, and parts of monoazo dyestufi, obtained by coupling diazotized Z-amino-l-hydroxybenzene-4-methyl sulfone and I-acetylamino-7-hydroxynaphthalene, in 333 parts by volume of formamide are heated with 16 parts of chromic 9 acetate, corresponding to 3.12 parts of chromium, in the presence of 15 parts of calcined sodium carbonate at 100105 until the starting dyestuffs have disappeared.

The chromium-containing dyestufi is then precipitated by the addition of sodium chloride solution, filtered off, washed with dilute sodium chloride solution and dried.

It is a dark powder which dyes wool from a Weakly acid to neutral bath in level olive grey shades of good fastness properties similar to those of the dyeings of the preceding examples.

10.6 parts of monoazo dyestutt from diazotized Z-amino-1-hydroxybenzene-4-ethylsulfone and acetoacetic acid-o-chloranilide and 9.65 parts of monoazo dyestutr' from diazotized 2-amino-1-hydroxybenzene-4-ethyl sulfone and 1phenyl-3-methyl-5-pyrazoloue in 350 parts of formamide are added at 8085 to 21.5 parts of formazane dyestufi, obtained by coupling equimolar amounts of diazotized '4-chloro-2-amino-l-hydroxybenzene with benzaldehyde phenyl hydrazone. 15 parts of sodium car-, bonate and 15 parts of cobalt acetate, corresponding to 3.54 parts of cobalt, are then added and the'whole is kept at this temperature until the metal complex formation is complete. The cobalt-containing dyestuft is precipitated by the addition of sodium chloride solution,- filtered OE and dried.

It is a dark powder 'which dyes wool from a neutral to weakly acid bath in olive shades. The dyeings have 16 similar good fastness properties as those obtained in the preceding examples.

Example 54 Cobalt complex OH HO OH I ] C-CHa N=NC=NNH SO2NH2 I] N=N(l) 0 I NH NO:

V SOzCzHg, Cl

21.2 parts of monoazo dyestulf from diazotized 2-amino-1-hydroxybenzene-4-ethyl sulfone and acetoacetic acid o-chloranilide in 350 parts of formamide are added at 80-85 to 11 parts of formazane dyestuff obtained by coupling an equimolar amount of diazotized 4-nitro- 2-amino-l-hydroxybenzene with benzaldehyde phenyl hydrazone-3-sulfonic acid amide, and 10.8 parts of formazane dyestuif obtained by coupling diazotized 4-chloro- Z-amino-l-hydroxybenzene with the same hydrazone. 15 parts of cobalt acetate, corresponding to 3.54 parts of cobalt, and 15 parts of sodium carbonate are added and the whole is kept at the above temperature until metal complex formation is complete. The cobalt-containing dyestuff is precipitated by the addition of sodium chloride solution, filtered off and dried.

It is a dark powder which dyes wool from a neutral to weakly acid bath in level olive green shades. The dyeings have good wet fastness and good light fastness properties.

Example 54a OzN 18.1 parts of formazane dyestufl obtained by coupling equimolar amounts of 4-nitr0-2-diazo1-hydroxybenzene with benzaldehyde phenylhydrazone and 15.5 parts of monoazo dyestuff obtained from 5 nitro-2-diazo-1-hydroxybenzene and 2 hydroxynaphthalene, are heated at 80-85 in the presence of 300 parts by volume of dimethyl formamide, with 15 parts of cobalt acetate (corresponding to 3.54 parts of cobalt), until no more starting dyestuffs can be traced.

The cobalt-containing dyestuif is precipitated by the addition of a concentrated sodium chloride solution, and is separated by filtration, washed with Water and dryed.

After drying, it is a dark powder which dyes spinning masses of cellulose acetate in navy blue shades.

2.6 parts of the cobalt complex dyestulf obtained according to the above example are added to 1000 parts of a solution of cellulose acetate dissolved in acetone containing 26% of dry cellulose acetate. To this mixture 20 parts of acetone are added and the whole is mixed by rotating in a well closed tumbler flask until the dyestuff has completely dissolved.

The dyed-spinning solution is then extruded through spinnerets and, after passing through a long heated tube,

in lieu of the combination of a forma'zane dyest'uff re.

15.4 parts of 4 nitro 2 amino-l-hydroxy'benzene are dissolved in 100 parts of hot water and 17.5 parts of concentrated hydrochloric acid,'the solution is cooled to and diazotized with a sodium nitrite solution (corresponding to 6.9 parts of sodium nitrite). The reaction actant with azo or azotneth ne dyestulf reactants used mixture is made neutral by the addition of SOdILIIII b1- therein, there is used an equivalent quantity of each of carbonate. The yellow diazonium suspension is stlrred at the forma'zane dyestuffs produced from the reactants given 0-3 into a solution of 28.8 parts of benzaldehyde phenyl in column II, III(a) and 111(5) of the following Table hydrazone-3'-sulfo'nic acid amide (produced conden- II by the procedure given in Example 55, infra, in comsation of benzaldehyde and phenyl'hydrazine 3 sulfonic binatioii with each of the azo dyestufls and azomethine acid amide) in 250 parts by volume of glycol monodyestuffs used in Examples 1 to 54 inclusive, other than methyl ether. those already used in combination with the respective The coupling mixture is then rendered and kept strongly forrnaZ-ane dyestuff of Table II, infra, in one of the prealkaline by the addition, at 04, of 5 N sodium hydroxide ceding examples; the corresponding cobalt metal mixed solution. On completion of the dyestuif formation, the complexes falling under Formulas IV and V, respectively, dyestuif is precipitated by the addition of 1000 parts by being thereby obtained. volume of saturated sodium chloride solution and filtered le 55 off. It is washed with dilute sodium chloride solution and v P is thus ready for use in a paste with water, cobalt acetate [Production of a formazane dyestuif exemplifying maksolution corresponding to' 3.54 parts of cobalt, and aning of formazanes falling under Formulas IIIA to IIIE]. other dyestuff reactant, as used in the preceding examples.

TABLE II M I II III IV .Hydr'azone fro'm Shade of 00 N o. Diazonium compound I complex on (a) Hydrazine (b) Aldehyde .wool 1 .4nitre-2-amino-l-hydroxybenzene Phenylhydrazine-B-sulioinic acid amide Benzaldehyde;

[III (b) being bonded in l-position at the benzene nucleus of III (a) J 2 Z-amino-l-hydroxy-benzene-4-sulfonic acld-N- Phenylhydrazine Benzaldehyde;

phenylamide-2,4,bis sulfonic acid amide. 3 4-phenylsulfonyl-2-aminophenyl-3-sulfonic .do .d0.- acid amide. 4 2-amin0-1-hydrcxybenzene-irsulionic acid-N- .do. .l... d0.

ethyl-N-phenylamide-4-sulf0nic acid amide. 5 3-amino-4-hydroxyacetophenone Phenylhydrazine-3-sulfonic acid amide. do. 6 5nitro-4-ethylsulfonyl-2-amlno-1-hydroxydo "do benzene. l 7 4-nitro-2-amino4-hydroxybenzene Phenylhydrazine-i-sulfonic acid amide do 8 Z-amino-l-hydroxybenzeueA-Sulphonic aeid- Phenylhydrazine a sulphonic acid amide do. Grey. Netihylphenylamide-4'-sulphonic acid .1111 H 9 4phenylsulphonyl-2-amino-i-hydroxyben- --.do ..do Do.

zenc 3-sulphonic acid amide. 10 4-nitro-2-amino4-hydroxybenzene "do Greenish-grey 2-amine-1-hydroxybenzenei-sulphonic aciddo Grey.

N -ethyl-N-phenyl-4 -sulphonlc acid amide. 12 l.- 2ami ro -l-hydroxybenzened-sulphonic acid do do Greenish-grey.

. 9- 111 9- 13 4-chloro-2-amino1-hydroxybenzene dc .do .L Grey. 14 2-ami 12101-hydr oxybenzenei sulphonic acid Phenylhydrazine 2,6dichlorobenzaldehyde Violet-grey.

21111 e. 4-nitro-2 amino-l-hydroxybenzene; do Do. .do 3,4-dichlorobenzaldehy Grey.

4-phenylsu1phonyl-2-amino'1-hydroxydo Butyraldehyde Reddish-grey.

benzene-3 -sulphonic acid amide. 18 2-amino-l-hydroxybenzene t-sulphonic acid- .do do Do.

N efihyl-N rphenylamideA sulphonic acid aml e. l9 4-chlorc-2-amiuo-I-hydroxybenzene. do do.- 0 Reddish blue grey. 20 4-phenylsulphonyI-Z-amlno-l-hydroxybenzene do Reddish-grey. 21 2-ami r(11o-1-hydroxybenzeneA-sulphonic acid do D0.

arm e. 22 2-amin c-1-hydrpxybenzene-i-sulphonic aciddo do Do.

N-methylamide. I 23 phenylsulphonyl-Z-amino-l-hydroxybenzene- 4-nitrophenylhydrazine Benzaldehyde Olive grey.

3'-sulphonic acid amide. 24 5-nitro-2-amino-l-hydroxybenzene Phenylhydrazine-ZK-sulphonic acid amide Blue-green. 25 2-amirdio-l-hydroxybenzene4-sulphonic acid 4-nitropl1enylhydrazinc Olive-green.

. 81111 e. Z'QmlIO-I-hYdIOXYbBIlZBIlG-l-SlllPhOHlO acid Phenylhydrazine-Zi-sulphouic acid amide Benialdehyde aml 9- 26 Plus Grey 2-amino-1-hydroxybenzenei-sulphonic acid do do methylamide. 27 4-ethylsulphonyl-Z-amino-l-hydroxybenzene .do D0. 28 do Pheuylhydrazine-3-sulphonic acid-N-methyl- Do.

. s N-B-hydroxyethylamide. 29 do Phenylhydraxine-B-sulphonic acid-B-hydroxy- Do.

. ethylamide. I 30 .do Phenylhydrazine-3-sulphonlc acid-N-ethylN- do... Do.

B-hydroxyethylamide. V 31 do Phenylhydrazine-4-sulphonic acid amide do Do. 32 do Phenylhydrazine4-sulphonic acid-N-methyldo Do.

N-flhydroxyethylamide. 33 do Phenylhydrazine-4-sulphonic acid-N,N-di-fl- .-do Do.

hydroxyethylamide. 34 4-nitro-2-amino-l-hydroxybenzene l-EIIlilO-l'lflphiihMGlle-L7'di-Sl1lphOnlC acid do Olive.

. amt e. 35 4-chloro-2-arnino-1-hydroxybenzenc do do.. Do. 36 4-nitro-2-amino-1-l1ydroxybenzene 4-methylphenylhydrazi Benzaglehyde-l-sulphonicacid Grey.

aim e. 37 do 4-methoxyphenylhydrazine .t. do .s Do. 38 4-1g1ethylsulphonyl-6-nitro-2-amino-1-hydroxy- Phenylhydrazine-3-sulphonic acid amide Benzaldehyde Green-olive.

enzene. 39 do Phenylhydrazine-4-sulphonic acid amide do Do. 40. 4,6-dinitro-2-amino hydroxybenzene Phenylhydrazine-3-sulphonlc acid amide do Do. do Phenylhydrazinc4-sulphonic acid amide Do.

, TABLE II.-Conti1iuc l I II III it Hydrazone from- I Shadeiof Co N 0. Diazonium compound complex on p (a) Hydrazine .(byAldehyde W001 105 do. 1-naphthy1hydrazine Benzaldehyde Olive-grey. 106 do Phenylhydr i-methyl-henzaldehyde Grey. 1: 107 .do do 4-methoxwbenzaldehyde.,- Do. 108 do 4-nitrophenylhydrazine Benzaldehyde"; Olive-grey. 109 do 3-nitrophenylhydrazinev l 7 do... Do.'. 110 4cgiloromethylsulphony1-2-amino-1-hydroxy- 4-nitrophenylhydrazine j d- Olive-green. enzene. 111 4-methylsulphonyl-Z-amino-l-ltydroxybenzene. 2,5'dichlorophenylhydrazine aa 2-6,dlchlorobenzaldehyde-..5- Violet. 112"-.. do .s d0 1 Benzaldehyde Grey vlolet 7. We claim: and cobalt as the common complexing' metal for both 1. A cobalt metal complex dyestuff which dyestufl conmoieties; sists essentially of a mixture of I '15 6. A 1:2 cobalt-metal complex dyestuif consisting es- (a) a bicyclically metallized dyestuif moiety selected sentially of the m'etal-complexed radical of the dyestuff from the group consisting of a monazo dyestulf of the formula moiety, a disazo dyestuff moiety and an azomethine (a) I dyestuff moiety, and 0H y no (b) a bicyclically metallized formazane dyestutf moiety; Y 4

said dyestuif moieties '(a) and (b) being complexed N=N by cobalt in a ratio of one cobalt atom for every two moles of dyestutf moieties; and the molar ratio of OaN (a) (b) ranging from 2:1 to 1:2. 2. A dyestufi as described in claim 1, wherein the ratio (b) the metal'complexed moiety of a dyestufl of the of (a):(b) is about 1:1. fmmula 3. A chromium metal complex dyestutf which dyestuif consists essentially of a mixture of (a) a bicyclically metallized dyestuif moiety selected from the group consisting of a monazo dyestuff I moiety, a disazo dyestuif moiety and an azomethine I110: SOzNHg dyestuff moiety, and

(b) a bicyclically metallized formazane dyestuff moiety; said dyestuif moieties (a) and -(b) being complexed by chromium in a ratio of one chromium atom for every two moles of dyestutf moieties; and the molar ratio of (a):(b) ranging from 2:1 to 1:2.

4. A chromium metal mixed complex dyestufl" which dyestutf consists essentially of (a) a bicyclically metallized dyestuff moiety selected 0 (a) from the group consisting of a monazo dyestulf OH HO moiety, a disazo dyestuff moiety and an azomethine dyestuff moiety, complexed in a molar ratio of 1:1 =N- and cobalt as the common complexing metal for both moieties.

7. A 1:2 cobalt-metal complex dyestufi consisting essentially of the metal-complexed radical of the dyestuff of the formula with chromium metal, the resulting chromium 1:1 complex being reacted with complex formation with (b) a bicyclically metallized formazane dyestuff, the

ratio of (a) to -(b) in the resulting mixed complex dyestuff being about 1:1. (b) the metal-complexed moiety of a dyestulf of the 5. A 1:2 cobalt-metal complex dyestutf consisting esfcrmllla sentially of the metal-complexed radical of the dyestulf H of the formula -N=NO=NNH I I N 03 SO2NH2 t t and cobalt as the common complexing metal for both 9 moieties.

8. A 1:2 cobalt-metal complex dyestuif consisting es- N=NC C*OHB sentially of the metalcomplexed radical of the dyestufi? of the formula S O2C'2Hs (b) the metal-complexed moiety of a dyestutf of the formula OH I H N=NC=N-NH 110-? I? N=Nooom N02 SOENH:

23 (b) the metal-complexed moiety of a dyestutf of the formula @N=NC=NNH 5 1 I N O: SOaNH:

24 (b) the metal-complexed moiety of a dyestuif of the formula I (IJOOH and chromium as the common compleXing-metal for both moieties.

N 0 references cited.

CHARLES B. PARKER, Primary Examiner.

R. J. FINNEGAN, D. M. PAPUGA, Assistant Examiners. 

